Process of producing chlorin and sulfate of sodium by catalysis.



H. B. KIPPER.

PROCESS 0F PRODUCING CHLORIN AND SULFATE 0F SODIUM BY CATALYSIS.

APPLICTION FILED JULY 5| l9l6.

Patented Jan. 29, 1918.

nue 'n fo@ NT www@ UNITED -STATES PATENT oFFIcE.

HERMAN B. mena, or NEW Yonx, N. Y?

PROCESS OF PBODUCING CHLOBIN SULFATE 02E' SODIUM BYA CATALYSIS.

Specification 'of Letters Patent. Patented an. v29, 1913.

Application mea my -5, 191e. seria; No. 107,502.

To all whom it may concern: y

Be it known that I, HERMAN- B. KIPPER, a

citizen of the United States of America, and

a resident of New York, county and State of New York, have invented certain newand useful Improvements in Processes of Producing Chlorin and Sulfate of Sodium by Catalysis, of which the following is a specification.v

This invention has reference to a novel process of producing chlorin gas and sodium sulfate. It consists essentially in the production of chlorin gas and sodium sulfate from surlfur dioxid and sodium chlorid in the presence of oxygen. These substances are made reactive by the presence o f a catalytic agent employed Ain a novel manner.

Chlorin gas is largely usedA in chemicalv manufacture. Great quantities of the gas are used inthe manufacture of bleaching powder. It is'used further in various chemi- -cal and analytical processes. The chlorin gas is produced by my novel process 1n a constant flowing stream and the resulting sulfate of sodium is purer than the commercial sulfate of sodium found on the market, therefore it is preferable in chemical manufacture. Furthermore, all the chlorin contained in the sodium chlorid employed is obtained whichqimplies cheap and slmple manufacture.

Heretofore chlorin gas has been produced during the electrolytic process -of produclng caustic alkalis. This process of manufacture is, however, expensive. Chlorin gas has also been produced by the manganese process in which manganese tetra-chlor1d is formed This unstable compound decomposes according to the formula v MnC14=MnClz.-|Cl2.

Thus only 50% of the chlorin contained in, the manganese tetra-chloridl is obtained which is naturally of disadvantage. A nother known process of -producing chlorin gas is based on the action of sulfur dioxid, water and atmospheric oxygen on sodium chlorid.

The stream of hydrochloric acid gas secured is very irregular. The gas is, therefore, irst absorbed or dissolved in sulfuric acid, from which, after saturation a constant flow of hydrochloric acid gas evolves. This method implies unnecessary chemical substances which increase labor and is therefore expensive. The hydrochloric acid formedis finally decomposed by oxygen in the presence of catalytic agents into chlorin and water,

In'order to overcome the defects herein described I employ a catalyst such as Aferric i oxid, cobalt oxid, nickel oxid, manganese dioxid, or cupric oxid or mixtures of catalysts. 'Ferrie oxid is preferred on account of its cheapness. It has been found that the chlorid, sulfur dioxid, and oxygen react in the presence of ferrie oxid at high temperatures to form chlorin gas and sodium sulfate.

The optimum temperature of this'rea'ction is between 400 and 600 C.

It is probable that chemical reaction actually takes place between the iron oxid usedv vas a catalyst and the reacting products somewhat according to the .following steps: It.

will be noted that the iron oxid, however, remains chemically unchanged after the'completion of the final reaction:

If desired the processl may befstarted di clusion of the reaction. If used in a finely divided form, the'iron oxid used as catalyst contaminates the sodium sulfate formed and is separated from the latter with considerable difficulty. In order to overcome this' difliculty, the catalytic agent is used as large solid lumps, or balls so that it can be readily separated Afrom the finely divided sodium sulfate. Y

In order to produce thesellumpsforballs,

I mix finely ground ferrie oxidand sodimm-4 sulfate.l The mixture' is then compressed and heated tothe fusion of the sodium. sulf' fate.

A further composition used is obtained from ferrie oxid Fe203, silicate of sodium Na2SiO3, and barium sulfate BaS04. l'llhis composition does not require heat for binding the lumps or balls together.

A third composition consists of ferrie oxid and cement, which composition in the shaped form is merely allowed to set.v

Another composition contains ferrie oxid, cement, andsodium silicate. This composition also is allowed to set.

The novel process may be carried out `in any suitable apparatus. One form of apparatus is diagrammatically illustrated in the accompanying drawing in which:

lFigure 1 represents in longitudinal central section with some parts in elevation an apparatus for carrying the present invention into eilect..

Fig. 2 is a cross section on line 2-2 of Fig, 1.

Fig. 3 shows mostly in sectional View a modified form of a detail part.

Similar characters of reference denote like parts in all the figures.

In the drawing a represents a closed cylinder preferably of iron sheeting which is centrally providethat one end, with an inlet tubeb and at the opposite end with a discharge tube e. The cylinder is rotatable by means of gearing d in a similar manner as ore roasting cylinders are revolved. vA tube e reaches into the inlet tube b and is secured therein by a. gasket f so that the tube e does not rotatebut is airtight therein. A hopper g with a. supply regulating valve 0"4 communicates with the tube e. Through the hopper the sodium chlorid is introduced in powdered form. rll`he tube e is somewhat bent upwardly beyond the hopper and sulfur dioxid is introduced through the same. The lumps or balls h acting as the catalyst or catalysts are placed into the cylinder so as to fill it about half. Near the inlet tube b on the inside of the cylinder end there is an iron flange z' which prevents the lumps or ballsv from entering the inlet tube o.

Within the 'cylinder and near the discharge tube c there is a flange j best shown in Fig. 2. 'llhe flange is secured with one end tothe inner surface of the cylinder.y llt is curved around the discharge opening and extends toward the inner cylinder surface for a certain' length. A channel iron k is mounted on the inner cylinder surface so thatits cud and the free end of the curved flange are in close proximity. During rota-- tion the sodium sulfate formed reaches this channelironand is thrown onto the curved flange from where it tallsout through the discharge tube o. cured to the rotating discharge tube o by l means oa gasket Z. 'llhe tube reaches into a housing m provided with a partition n,

@o and an outlet tube o. The tube [t1 is pero- A stationary tube k1 is senaartoe@ rated so as to allow the chlorin gas formed to pass out in the direction of the arrows. 'llhe chlorin finally passes out through the outlet tube o. 'lho sulfate oit' 'sodium is col-- lected in a vessel y) which may be inserted and removed through the door g.

lin place of the curved Hange j a spiral arrangementll may be employed which transportsthc sulfate ot sodium to the discharge tube c. ln either case the curved flange or spiral device are covered with net work as indicated at s in lFig. 2 for the purpose ot preventingl the lumps or balls from entering the discharge section ot the apparatus or leaving the cylinder. Any sulfate oit' sodium mixed with the solid linups or balls is easily separated in a mechanical manner.

The sulfate dioxid gas and an`l excess of air enter the reaction cylinder a at a temperature of approximately 000o C. The

cylinder a is also externally heated. The.

process of producing chlorin and sulfate ot' sodium is initiated and propagated at a temperature of from 200 to 900o C. but

takes place uniformly at a temperature of about 600o C. within the cylinder or drum by means of a catalystI or catalysts and the resulting gas and salt discharge through thi` discharge tube.

llt will be noted that in the present process of' producing chlorin gas and sulfate of sodium a solid substance and gases are made to react in the presence oil-a moving catalytic substance which moves during the rotation of the drum or cylinder. The power of such substance for catalytic action is increased by the actual motion of the catalyst. This feature of the presen process is entirely novel.

ll claim as my invention:

1. 'llhe process of transforming sodium chlorid. sul-fur dioxid and oxygen into chlorin and sodium sulfate in one continuous operation which comprises mixing a catalyst with the sodium chlorid, applying heat, agitating the mixture and bringing sulfur dioxid and oxygen into contact therewith.

2. 'll`he proce-ss oit transforming sodium chlorid, sulfur. dioxid and oxygen into chlorin and sodium sulfate in one continuous operation which comprises mixing a catalyst with the sodium chlorid, heating the mixture to a temperature of from 200 to 900 C.. agitating the mixtlu-e and bringing sulfur doxid and oxygen into contact therewith.

'llhe process of transforming sodium chlorid, sulfur dioxid and oxygen into chlorin and sodium sulfate in one continuous operation which comprises mixing a catalyst with the sodium chlorid, maintaining this mixture at a temperature oft approximately 600 C.. agitating the` mixture and bringing snolltiir dioxid and oxygen into contact there- Wl v lill@ 4. The process of ltransforming sodium chlorid, sulfur dioxid and oxygen 1nto chlorin and sodium sulfate by catalysis in one continuous operation which comprises.

mixing ferric oxid with the sodium chlorid, applying heat, agltating the mixture and bringing sulfur dioxid and oxygen into con-4 chlorid, sulfur dioxid and oxygen into chlorin and sodium sulfate by catalysisin one continuous operation which comprises mixing a catalyst in form of lumps, composed of ferrie oxid and a binding mineral substance, with the sodium chlorid, maintaining this mixture at a temperature of approximately 600 C., While agitating it and bringing sulfur dioxid and oxygen into contact therewith.

7.-The process of transforming sodium chlorid, sulfur dioxid and oxygen into chlorin, and sodium sulfate which comprises mixing a catalyst existing in the form of lumps, composed of ferrie oxid and sodium sulfate, with the sodium chlorid, maintaining this mixture at a temperature of approximately 600 C., while agitating it, and bringing sulfur dioxid and oxygen into contact therewith.

8. The process of transforming sodium chlorid, sulfur dioxid and oxygen into a constantly flowing stream of chlorin gas and sodium sulfate by catalysis consisting in mixing lumps, composed of ferrie oxid and sodium sulfate with the sodium chlorid, propagating the reaction at approximately a temperature of 600 C..l While agitating this mixture, collecting the sodium sulfate formed, and conducting the chlorin gas away.

9. In the process of transforming sodium chlorid, sulfur dioxid and oxygen intochlorln and sodium sulfate, the step of mixing a catalyst with the sodium chlorid, heat- 1n g thls mixture, agitatlng 1t,l brmgmg sulfur dioxid and oxygen into contact with the mixture and propagating the reaction by means ofthe moving catalyst therein.

Signed at New York, N. Y., this 20th day of June 1916.

` l HERMAN B. KIPPER. Witnesses:

HENRY STEINMETZ, LILLEY E. SCHMIDT. 

